Unsaturated carbamates



United States Patent" UNSATURATED CARBAMATES Donald W. Kaiser, Old Greenwich, Conn., assignor to American Cyanamid Company, New York, N. Y., a corporation of Maine No Drawing. Original application July 26, 1947, Serial No. 106,977, now Patent No. 2,647,916, dated August 4, 1953. Divided and this application May 27, 1953, Serial No. 357,928

4 Claims. (Cl. 260-482) This application is a division of my copending application Serial No. 106,977, filed July 26, 1949, now Patent Number 2,647,916, dated August 4, 1953. The invention claimed therein relates to a new and improved method of preparing certain N-substituted carbamates. More particularly it is concerned with the method of preparlng an N-substituted carbamate which comprises effecting simultaneous reaction under heat between (1) an alkali-metal cyanate, more particularly a cyanate of sodium, potassium, lithium, rubidium or caesium, (2) a hydrocarbon halide (active hydrocarbon halide) represented by the formula RX, where X represents halogen (e. g., chlorine, bromine, iodine) and R represents a radical selected from the class consisting of alkyl (including cycloalkyl), alkenyl (including cycloalkenyl), aralkyl and aralkenyl radicals, and (3) an alcohol selected from the class consisting of monohydric and dihydric alcohols, e. g., methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert.-butyl, amyl, isoamyl, sec.-amyl, hexyl, cyclohexyl, cyclohexenyl, heptyl, octyl, nonyl, decyl, allyl, methallyl, m-chloroallyl, hexenyl, octenyl, benzyl, cinnamyl, etc., alcohols, ethylene glycol, diethylene glycol, triethylene glycol, etc., preferably such an alcohol which is normally a liquid, that is to say, a monohydric or dihydric alcohol of such relatively low molecular weight that it is a liquid at a temperature of the order of 30 C. or lower. The N-substituted carbamate which is thereby produced is then isolated from the resulting reaction mass.

When a monohydric alcohol is employed the desired products of the method may be represented by the formula where R has the same meaning as given above with where each R has the same meaning as given above with reference to Formula I and R" represents a divalent radical corresponding to that present in the dihydric alcohol,

which latter may be represented by the formula \OH Another product of the reaction when a dihydric alcohol is one of the reactants is a carbamate which may be represented by the formula III III R-N-( J--OROH where R and R" have the same meanings as given above with reference to Formula II. u

The invention claimed in the present divisional appll apparatus used, and other influencing factors.

2,697,720 Patented Dec. 21, 1954 cation is separate and distinct from that claimed in the parent copending application. More particularly the invention claimed herein is directed to new unsaturated carbamates, and still more particularly to new N-substituted carbamates of the class-consisting of allyl N-allylcarbamate, B-hydrovyethyl N-allylcarbamate and ethylene bis- (N-allylcarbamate).

It was known prior to my invention that carbamates of the kind embraced by Formula I could be prepared by the addition of a monohydric alcohol to an isocyanate or by reaction between a chlorocarbonate and an amine, but the resulting carbamates are costly due, for one reason, to the relatively high cost of the isocyanate or amine reactants used in their preparation. Furthermore, both the isocyanates and the chlorocarbonates constitute a health hazard to workmen when these materials are employed in chemical reactions.

The invention claimed in parent application Serial No. 106,977, new Patent Number 2,647,916, is based on my discovery that N-substituted carbamates of the kind embraced by Formulas I, II and III can be produced in adequate yields from relatively inexpensive, non-toxic materials as briefly described in the first paragraph of this specification and more fully hereafter. More particularly I have found that such N-substituted carbamates can be prepared by heating under atmospheric pressure or, preferably, under superatmospheric pressure, e. g., at pressures ranging from 20 pounds to 10,000 pounds or more per square inch, and at a temperature within the range of about C. to about C., or a little higher, e. g., about 200 C. a mixture containing the ingredients described under (1), (2) and (3) in the first paragraph of this specification. Reaction at atmospheric pressure, e. g., by heating at such pressure under reflux at the boiling temperature of the reaction mass, is generally less satisfactory from a practical standpoint. The reaction mass is preferably agitated, e. g., by mechanical stirring, during the'reaction period, which may range, for instance, from V2 hour to 24 hours or longer, depending upon the size of the batch, the reactants and molar proportions thereof which are employed, kind of cases wherein the alkali-metal cyanate, e. g., potassium cyanate, is not completely soluble in the reaction mass, an inert (i. e., inert during the reaction) solubilizing agent is advantageously incorporated into the reaction mass for improving or increasing the solubility of the alkali-metal cyanate therein. Inert, non-hydroxylated solubilizing agents can be employed for this purpose, acetonitrile being especially suitable for use. Examples of other solubilizing agents that can be used, although less effective than acetonitrile, are propionitrile, fl-methoxypropionitrile, dimethylcyanamade, acetone, dioxane and nitrobenzene.

When a monohydric alcohol is employed and taking potassium cyanate as illustrative of the alkali-metal cyanate, the reaction may be illustrated by the following equation:

IV E

where X represents halogen, e. g., chlorine, bromine or iodine and preferably chlorine, and R and R have the same meanings as given above with reference to Formula I. The reaction probably proceeds through stages which may be represented by the following equations:

There is also some evidence that a side reaction leading to the formation of an unsubstituted carbamate occurs. It is conceivable that this side reaction takes place through several stages which may be illustrated by the following equations:

The above views are supported by the fact that the larger In those the amount'ofmonohydric alcohol (e. g., methanol) employed, the 1arger-- (otherconditions being the samey isv the amount of N-unsubstituted carbamate that is formed.

The mechanism of the reaction is probably of the same general .character; when -a-'-dihydric. alcohol-is useddmplace of; a1. monohydric. alcohol, the: products: of. the: reaction including, a; his carbamate. (see' Formula. II),- as- :the: main productand a.- hydroxy derivative (see Formula -.III.'),-- as another product.

The-weight of the evidence indicates&that,-.in the method of my invention, the alkali-metal cyanate functionstboth as anzacidlhydrohalide) acceptor andlas a substance:capable. of reaction-withlan active:hydrocarbon'halide of thekindi previously; described, e. g, benZyL-phenylethyl and .other. aralkyl chlorides, bromides and iodides; methyl, ethyl,- propyl, isopropyl, butyl,.amyl, isoamyl', hexyl, hep.- tyl;. octyl, nonyl, decyl and other; alkyli chlorides;.bro-- mides and:iodides; allyl, methallyl, crotyl, pentenyl,,etha1lyl,,.hexenyl, heptenyl, octenyl and other. alkenyl. chlorides bromidesand iodides; and.alpha-pheny lallyl' and other aralkenyl chlorides, bromides and. iodides.-

It Wasquite: surprising, andMneXpectedthatan' alkali metal-cyanate, an. active. hydrocarbonhalide of thekind described under. (2,) of the first paragraph hereintandsan alcoholof. the kind described under (3.)-of; the first parae graphiof. this'specificationtcould. be caused-to react .to.-. gether. to. yield the aforementioned .N-substituted carbam: ates; since. ordinarily;- it: would be. expectedlhat, if. any; reaction occurred, .the reaction might take: the following course;to-yield.an. iminocarbonate. IntEquations X and XI the-- cyanateis shownfor purposeof illustration as potassium cyanate.

The: molar ratios ofreactantsmay be varied fairly, widely, since the excessover stoichiometrical proportions ismerelypresent in the reaction mass. as unreacted. or partly, reacted zmaterial. For. example, all of the reactants can be usedin equal. molar proportions, or. with the alkaliwmetal cyanate or the! hydrocarbon halide. in: ex-. cess.ofi the. other, e. g.,,from 0.5 to 25or. 3.0 molepen cent;, or." evenas. much. as 1 50. mole per cent, .of. the one imexcessof the other. The alcoholireactanttcanzbe used irL a.-molar. amount which .is-the sameas thatof.:the= other. reactants,'-,or ittcan be; employedinexcess of either, .e: g". from.0'.5 to. 25.00 01*3000 mole per. cent.in.excess.- The use. ofi even larger amounts of! alcohol reactant; is not precluded, especiallywhcn: larger yields of. an:.N=unsubstitutedxcarbamate are.desired.-. Good. results havebeen obtained by using the alcohohreactant in' a-molar. amount correspondingtofrom 2.to' litimes-.the molar. amount of falkali-metal. cyanate t employed. When: a: dihydric. alcohol is used, it can be employedin stoichiometrical pro.- portions with either the alkali-metal cyanate or the.hy, drocarbon= halide, or. intexcess thereof as has been .mentioned above.

In.order: thatthose skilledin-the art; better. may -understand how the present invention can be carriediinto effect, the following examples are given by way ofillus tration and not by way of limitation. All parts and percentagecar'e by weight.

Examplel.

" A prox;

i Pam: lilolar Ratios.-

Benzyl chloride 126. 1.10 Potassium cyanate 81. 1 1. 0 Methanol 398. 0 12. 4

wereheated. and .agitatedrtogether under reflux.at.the .bbil; ing,temperature-ofthenmass.for 10.1mm. The excess methanol was. distilled. offi under. reduced pressure,, the. residue was filtered to remove the K'CI' (b'y-prodilcLof the reaction),,,and the oily filtrate was distilledi Solid separated inttlie-distillate; which boiledwithin the range of 163 166 C.,.d1'1ring distillation. Thetotal distillate weighed 61: partsand wasmostly: benzyl. methyl ether. Filtration of.the distillate. yielded 17 parts of crystals, which werewash'edwith' hexane.- The purifiedcrystal's melted at 6465 C., which is the recorded melting point for-.methyl-N-benzylcarbamate.-

Example 2 Approx. Parts Molar Ratios Potassium-cy anate.(94.27 86. 0 1. 0 Ally] c-..1orid.- .f. 76. 5 1. o Methanol. 159. 2' 4. 97

A; mixture. of the. above. ingredients." was heated. and agitatedtfortlhourstat 15.0 G.. inan autoclave under superatmospheric.pressure; The.solid:which was filtered from the cold reaction mass containedonly-a trace of potassium cyanate. After strippingthe low-boiling fraction from the filtrate;- th'e residue:was.distilled under reduced pressure. There was obtained 75.5 parts of colorless liquidlwhich boiled atz78't" C.'. at: 141mm: This-cor- I'CSPOHdSitOl a' yield of1'65 .6%- oflcrude' methyl: N allylcarbamate. Analysis: oft this crude product. for: nitrogen; without? furthenpurifioation, gave. the following results:

Per. cent N Calculatedfor. CSHOzNL 1217 Found 13175 The". methyl: carbamate: which: was: present 2 in the. crude productwas: isolated: by. dilutingzther'crude product with benzene, washing: the: benzene.- solution: with. water; and then: evaporating :thei aqueous extract to; dryness:

Example. 3-

This' example: illustratestlie. use of an inert solubilizing agent, specificallyacetonitrile,for improvingthe solub'ilit'y; of. the alkali-metal cyanate; specifically potassium cyanate; in the reaction mass.

-. Approx; Ports Molar Ratios Percent N- Calculatedi forsCHeO'zN: 12.17 Found 12.55

Using a short head, the residue from the above distillation was distilled under a pressure of 0.5 mm. The

material boiledJoverrarangeof l40 C., and 15 parts of.amixture of.triallyl isocyanurateand diallylurea was..ob'tained;, the. latterv probably being; formed as the result. of'I the. presence; of 1 a. slight quantity. of water, according to. thefollowing equation:

XII RNCO H2O RNH: CO2

The? triallyli iso'cyanurate undoubtedly resulted from tri-. merization of ally1= is'ocyanate before it reacted with the alcohol.

Additional examples involving the use of potassium. cyanate, allyl chloride and methanol,,and in which the reaction conditions and proportions of reactants were varied, are-:givemhereinafter; The term crude product" with reference to yield means=that methyl earbamatmwas notzseparatedfromdlie product:

lowing:

Per cent N Calculated for CsHsOzN 12.17 Found 12.55

The refractive index of the thusly purified sample was 1.4463 at 25 C.

Example 5 Approx. Parts Molar Ratios Potassium cyanate (94.2%) 86. 1 Allyl chloride 76. 1 "Methanol 159. 2 4. 97

Conditions of reaction.-Heated with agitation in an autoclave under superatmospheric pressure for 5 hours at 125 C.

Results.Distillation at a pressure of mm. gave 70 parts of liquid which distilled at 7476 C. No solid separated in the condenser. The yield of crude product was 61%.

Example 6 Same as in Example 5 with the exception that 79.6 parts of methanol was used. Distillation yielded 52.5 parts of distillate boiling at 80-90 C. at -16 mm. pressure. The residue amounted to 10 parts. The yield of crude product was 45.6%

Example 7 Same as in Example 5 with the exception that about 107.5 parts (about 1.25 moles) of 94.2% potassium cyanate was employed. Upon distillation there was obtained 63.2 parts of liquid containing a small amount of solid. The distillate boiled at 67-72 C. at 10 mm. pressure. The yield of crude product was 55%.

Example 8 Same as Example 5 with the exception that the reactants were heated with agitation in an autoclave under superatmospheric pressure for 1 hour at 150 C. Distillation 75 parts of crude product in a yield of 65%. Extraction with water gave 6 parts of methyl carbamate. A nitrogen analysis of the salt (KCl) which was separated from the reaction mass indicated the presence of only a slight amount of unreacted potassium cyanate.

Example 9 Same as in Example 5 with the exception that about 95.6 parts (about 1.25 moles) of allyl chloride was used. Upon distillation there was obtained 70 parts of liquid boiling at 66-69 C. at 9 mm. pressure. A large amount of black resinous material remained as a residue. The product was diluted with benzene and washed with water. Evaporation of the washings yielded 7 parts of methyl carbamate. The yield of crude product was 61 Example 10 Same as in Example 6 with the exception that the reactants were heated with agitation in an autoclave under superatmospheric pressure for 3 hours at 150 C. After removal of the excess methanol by distillation, the resulting reaction mass was very dark in color and contained a large amount of solid material. It was therefore diluted with benzene and washed with 60 parts of water. Dis tillation of the diluted and washed material yielded 49 parts of liquid which boiled at 67 C. under a pressure of 10 mm., leaving about 1520 parts of a tarry residue. Evaporation of the washings gave 11 parts of solid material (mainly methyl carbamate). The yield of purified methyl N-allylcarbamate, that is, product from which methyl carbamate had been separated, was 42.6%.

Example 11 Approx. Parts Molar Ratios Potassium cyanate (94.2%) 43.0 1.0 Allyl chloride 42. 0 1. 1 Methanol 79. 6 4. 97

The allyl chloride was added to the mixture of potassium cyanate and methanol heated to about C. over a period of 35 minutes under a pressure of about 180 to 220 pounds per square inch, after which the reaction mass was heated for an additional 25 minutes at the same temperature under a pressure of about to 187 pounds per square inch. After removal of the excess methanol the resulting dark and viscous reaction mass was treated with benzene and water as described under Example 10. Distillation yielded 18.6 parts of methyl N-allylcarbamate. The yield of purified material was 32.6%.

Example 12 Approx. Parts Molar Ratios Potassium cyanate (94.2%)... 86.0 1. 0 Ally] chloride. 84. 5 1. 1 Methanol 159. 2 4. 97 Water 10. 0 0. 55

The mixture of the above reactants was heated with agitation in an autoclave under superatmospheric pressure for 1 hour at 150 C. The resulting reaction mass was filtered, and the methanol was removed from the filtrate by distillation. The filtrate was diluted with benzene and washed with water. Distillation of the benzene solution yielded 27.6 parts of methyl N-allylcarbamate. Evaporation of the aqueous solution yielded 21.5 parts, which corresponds to a yield of 28.7%, of methyl carbamate. The yield of purified methyl N-allylcarbamate was 24%.

Example 13 Same as in Example 10 with the exception that 119.4 parts of methanol was used instead of 79.6 parts as in Example 10, and the reaction mass was heated at 150 C. for. only 1 hour. Distillation of the reaction mass yielded 70.7 parts of liquid boiling at 70-72 C. under a pressure of 16 mm. The product was dissolved in about 88 parts of benzene, and the resulting solution was washed with 50 parts of water. The yield of crude product was 61%. Distillation of the washed, benzene solution of the product gave 51.5 parts of methyl N-allylcarbamate, which corresponds to a yield of 45% of purified material.

The mixture of the above reactants was heated in an autoclave for three hours at 150 C. Distillation of the resulting reaction mass yielded the following cuts:

(1) 53 parts, B. P. 7881 at 12 mm.; and (2) 14 parts, B. P. 105120 at 0.5 mm., which was a mixture of diallylurea and triallyl isocyanurate.

The yield-of purified methyl N-allylcarbamate was 46%.

Example 15 out 1 3 l fi f Parts ill l Approx. '5 I Allyl N-allylcar- 61-85 1.5-0.25 96 68 Parts Molar bamate.

Ratios II Triatllyl isocyanu- 91-109 0.25 4

re 6. III Diallylurea 110440 0.25 7 Sodium cyanate 65. 1. 0 Allylehloride 80.5 1.05 10 2 Cut I-was redistilled to obtain a purer form of allyl mmnimle 2 N-allylcarbamate, .B. P. 69-73 c. at 0.05 mm., which The conditions of reaction in this example were the same as those described under Example 14. Some unreacted sodium cyanate remained in the reaction mass. Upon distillation there was obtained 25.5 parts of liquid boiling at 7679 C. under a pressure of 13 mm. The yield of purified methyl N-allylcarbamate was 22%.

Example 16 This example illustrates the preparation of n-butyl N-allylcarbamate.

Approx. Parts Molar Ratios Potassium cyanate (94 2%) 86.0 1. 0 Ally] chloride. 80. 5 1. 05 n-Butauol 148; 0 2.0 Acetonitrile 313. 1 7. 64

The mixture of the above ingredients was heated with agitation for 3 hours at 150 C. in an autoclave under superatmospheric pressure. After filtering oi the solid, the filtrate was distilled'to obtain the following fractions:

Pressure, Cut B. P., G. 1mm Parts I 108-112 84. 5 II 82-105 0. 15 11. 5 III 110-130 0. 15 5. 0

Cuts I and II were combined and redistilled to obtain the following cuts:

out -5. eas

Cut B comprising mainly n-butyl N-allylcarbarnate was redistilled. Analysis of a middle fraction for nitrogen gave the following results:

Percent N Calculated for C8H1502N 8.92

Found 8.87

Example 17 This example illustrates the preparation of allyl N-allylcarbamate. As in the previous example, acetonitrile was used to increase the solubility of the potassium cyanate were carefully .dried and then heated together in an autoclave for 3 hours at 150 C. under a pressure of about 140 pounds per square inch. The solid was filtered off, and theifiltrate was distilled to obtain the following highboiling fractions:

gave the following nitrogen analysis:

A mixture of the above ingredients was heated and agitated in an autoclave under superatmospheric 'prcsure for 3 hours at 150 C., yielding. a light-brown reaction mass. The salt which was filtered from'this mass contained a considerable amount of unreacted potassium cyanate. Distillation of the filtrate gave 82 parts (44% yield) of crude n-hexyl N-allylcarbamate which boiled at -107 C. at 0.05 mm. The crudeproduct was purified by redistillation to yield a product boiling at 97 C. under a pressure of 0.05 mm. .and showing the following upon analysis for :nitrogen:

Percent N Calculated for C1oH19O2N 7.57 Found 7.43

Example 19 This example illustrates the preparation of fl-hydroxyethyl N-allylcarbamate, the formula for which is Approx.

Parts Molar Ratios Potassium evanate 81.0 1. 0 Ally] chloride 76. 5 1.0 Ethylene glycol 278. 9 4. 5

The allyl chloride was added from a dropping funnel over a 2-hour period to a stirred mixture of the potassium cyanate in the glycol at a bath temperature of 100l35 C. The mixture was then heated at C. for 40 minutes. The white crystalline salt which was filtered from the hot reaction mass contained no potassium cyanate.

The excess glycol was removed from the filtrate under reduced pressure, the distillate boiling at 109 C. at 20 mm. pressure. From the remaining reaction mass there was obtained 43 parts of'liquid boiling within the range of 90-l47 C. under a pressure of 0.25 to 1 mm. This'liquid fraction was redistilled using a Vigreuxcolumn. Cut I boiled at 65 -99 C. under a pressure of 0.35 to 0.2 mm. Cut H, which was fairly pure p-hydroxyethyl N-allylcarbamate, boiled at 99.5 l08 C. under a 'pressure of 0.2 mm. -It was soluble in water in all proportions. An analysis of Cut II for nitrogen gave the 'following results:

Percent Calculated for CsHiioaN 9.66 Found 9.92

Example 20 This example illustrates the preparation of ethylene b1s(N-allylcarbamate), the formula for which is The reaction between the above ingredients was carried out at 150 C. for 3 hours under a pressure of about 100 pounds per square inch while agitating the mass. The reaction mass was filtered and the filtrate distilled at a slightly reduced pressure until the acetonitrile was removed. An equal amount of benzene was mixed with the residue. Attempted extraction with 62 parts of water gave complete solution and, therefore, 200 parts of henzene was added. The two layers were separated after the mixture had been neutralized with a few drops of acetic acid. The benzene solution was distilled, giving the following fractions after the removal of benzene:

Cut Pressure, Parts Product 129-162.- 0.15-0.25 Ethylene his (N-allylcarbamate). Residue. approx. 5.0.-

The water was distilled from the aqueous portion, leaving 21 parts of material which distilled as follows:

Cut B. P., 0. Pressure, Parts Product A 60 0.1-0.2 3.5 Glycol. B 113-128 0.2-0.3 10.0 B-hydroxyethyl N-allylcarbamate. O Residue..- 5.0 Ethylene bis(N-allylcarbamate).

Fraction II was redistilled giving 16 parts of liquid, B. P. 1l5-ll8 C. at 0.15 mm., which was soluble in both benzene and Water and gave the following analysis:

Percent N Calc. for ,B-hydroxyethyl N-allylcarbamate 9.66 Calc. for ethylene bis(N-allylcarbamate) 12.28 Found 10.3

This fraction was probably a mixture of the two carbamates. There was also obtained from Fraction II 5.5 parts of ethylene bis(N-allylcarbamate).

The total yield of ethylene bis(N-allylcarbamate) was 47 parts or 41% of the theoretical. Crystalline plates were obtained from hot water in which it was less than 10% soluble. A sample which had been crystallized from a cyclohexane-benzene mixture melted at 100 C. and gave the following analysis:

The mixture was heated and agitated for 3 hours at 1'0 150 C. in an autoclave under superatmospheric pressure, and then worked up as in the preceding run. There was obtained a 56% yield of ethylene bis(N-allylcarbamate) and a 20% yield of ,B-hydroxyethyl N-allylcarbamate.

Example 22 A prox Grams lolar Ratios Potassium cyanate (100 mesh) 40. 6 0.5 Benzyl chloride 63. 4 0. 5 Methanol (anhydrous) 395. 0 12. 3 Magnesium salt of dlootyl sulfosucoinate (wetting agent) 0.3

The finely divided potassium cyanate and the aforementioned wetting agent were added to the methanol, after which the mixture was stirred for 30 minutes in a reaction vessel placed in an oil bath maintained at about 85 C. The benzyl chloride was then added to this mixture over a period of 30 minutes, after which the mixture was heated with agitation under reflux (bath temperature of -100 C.) for 7 hours. The salt was filtered off and washed with 25 ml. of methanol, and the filtrate was concentrated to ml. and again filtered. Distillation gave 59 grams of colorless distillate, B. P. 162-170 C. The distillate was treated with 25 ml. of hexane, chilled to 0 C., filtered, chilled to -20 C. and again filtered. The yield of methyl N-benzylcarbamate, m. p. 5862 C., thereby obtained was 16.5 grams, which corresponds to 20% of the theoretical. The liquid residue distilled at 77-85 C. at 24 mm. pressure and consisted mainly of benzyl chloride plus some benzyl alcohol.

It will be understood, of course, by those skilled in the art that my invention is not limited to the particular reactants, proportions thereof, solubilizing agent and proportion thereof, nor to the conditions of reaction, as given in the foregoing examples by way of illustration. Thus, instead of potassium cyanate or sodium cyanate, any of the other alkali-metal cyanates can be used; and instead of benzyl chloride or allyl chloride, any other active hydrocarbon halide, more particularly an active alkyl, aralkyl, alkenyl or aralkenyl chloride, bromide or iodide, numerous examples of which have been given hereinbefore, can be used. Also, instead of methanol, n-butanol, n-hexanol, allyl alcohol or ethylene glycol, I can use various other monohydric or dihydric alcohols, preferably a normally liquid monohydric or dihydric alcohol, numerous examples of which have been given hereinbefore. Additional examples of such alcohols are crotyl alcohol, 3-hydroxy-l-butene, 2-cyclopentenol, 2- cyclohexanol, 1-hydroxy-2,3-butadiene, 3-chloro-2-butene-l-ol, phenylethyl alcohol, isooctyl alcohol, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monophenyl ether, diethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol ethylbutyl ether, diethylene glycol monobutyl ether, propylene glycol, dipropylene glycol, ethylhexanediol, polyethylene glycols having the general formula HOCH2 (CH2OCH2) nCH2OH where n is a value such that the glycol has an average molecular weight ranging from about 200 to about 700, 2 methoxymethyl 2,4 dimethylpentanediol 1,5, 2 ethoxymethyl 2,4 dimethylpentanediol 1,5, butanediol-l,3(butylene glycol), octylene glycol, pentamethylene glycol, decamethylene glycol, 2-butene-l,4- diol, etc. Additional examples of unsaturated alcohols that can be used are given in Pfann and Kropa Patent No. 2,609,358 dated September 2, 1952, and which matured from application Serial No. 738,736, filed April 1, 1947 The use of monohydric and dihydric alcohols of higher molecular weight than those mentioned herein by way of example is not precluded, but, in general, the higher-molecular-weight alcohols which are not normally liquids at 30 C. or lower are less satisfactory for use because of the greater difficulty in dissolving the alkalimetal cyanate in the reaction mass containing such higher boiling alcohols of higher molecular weight.

In my copending application Serial No. 357,927, filed concurrently herewith, claims are made to triallyl iso- 

1. AN N-SUBSTITUTED CARBAMATE OF THE CLASS CONSISTING OF ALLYL N-ALLYLCARBAMATE, B-HYDROXYETHYL N-ALLYLCARBAMATE AND ETHYLENE BIS(N-ALLYLCARBAMATE). 